Naslov
Sterically Congested Adamantylnaphthalene Quinone Methides

Autori
Veljković, Jelena ; Uzelac, Lidija ; Molčanov, Krešimir ; Mlinarić-Majerski, Kata ; Kralj, Marijeta ; Wan, Peter ; Basarić, Nikola

Izvornik
Journal of organic chemistry (0022-3263) 77 (2012), 10; 4596-4610

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
adamantanes ; antiproliferative activity ; laser flash photolysis ; naphthols ; photodehydroxylation ; proton transfer ; quinone methides

Sažetak
Five new (2-adamantyl)naphthol derivatives (5-9, quinone methide precursors, QMP) were synthesized and their photochemical reactivity investigated by preparative photolyses, fluorescence spectroscopy and laser flash photolysis (LFP). Excitation of QMP 5 to S1 leads to efficient excited state intramolecular proton transfer (ESIPT) coupled with dehydration, giving quinone methide QM5 which was characterized by LFP (in CH3CN-H2O, λmax = 370 nm, τ =0.19 ms). On irradiation of QMP 5 in CH3OH-H2O (4:1), the quantum yield of methanolysis is Φ = 0.70. Excitation of naphthols QMP 6-8 to S1 in CH3CN leads to photoionization and formation of naphthoxyl radicals. In a protic solvent QMP 6-8 undergo solvent-assisted PT giving QM6 or zwitterion QM8 that react with nucleophiles delivering adducts, but with a significantly lower quantum efficiency. QMP 9 in a protic solvent undergoes two competitive processes, photosolvolysis via QM9 and solvent-assisted PT to carbon atom of the naphthalene giving zwitterion. QM9 has been characterized by LFP (in CH3CN-H2O, λmax > 600 nm, τ =0.9 ms). In addition to photogenerated QMs, two stable naphthalene QMs QM10 and QM11 were synthesized thermally and characterized by X-ray crystallography. QM10 and QM11 do not react with H2O but undergo acid-catalyzed fragmentation or rearrangement. Antiproliferative activity of 5-9 was investigated on three human cancer cell lines. Exposure of MCF-7 cells treated with 5 to 300 nm irradiation leads to enhanced antiproliferative effect, in accordance with the activity being due to the formation of QM5.

Izvorni jezik
Engleski

Znanstvena područja
Kemija, Temeljne medicinske znanosti

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